Ammonia Leakage from Refrigeration Plant and the Management Practice

R.K. Gangopadhyay and S.K. Das Chemical Engineering Department, University of Calcutta, Kolkata 700 009, India; drsudipkdas@vsnl.net (for correspondence)
Published online 13 July 2007 in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/prs.10208
This article deals with the two incidents of ammonia leakage in industries situated in West Bengal, India, and the probable causes of the accident and the ensuing sequence of events. Emergency procedures are also discussed. Ó 2007 American Institute of Chemical Engineers Process Saf Prog 27: 15–20, 2008 Keywords: ammonia; leakage; oil separator; hazard; emergency procedures ammonia varies widely between individuals, and the dose-response effects described above are likely to be those experienced by the more susceptible members of the population. Henderson and Haggard [1] tabulated (Table1) the physiological response of ammonia. Ammonia is absorbed in the human body by inhalation, ingestion, and probably percutaneously at concentrations high enough to cause skin injury. Data are not available on absorption of low concentrations through the skin. Once absorbed, ammonia is converted to an ammonium ion as the hydroxide and as salts, especially as carbonates. The ammonium salts are rapidly converted to urea, thus maintaining an isotonic system. Ammonia is also formed and consumed endogenously by the metabolism and synthesis of amino acids. Excretion is primarily by way of the kidneys, but an insignificant amount is passed through the sweat glands. The National Institute for Occupational Safety and Health (NIOSH) recommended time-weighted average (TWA) for anhydrous ammonia is 25 ppm (18 mg/m3) and the short-term exposure limit (STEL) is the same [2].
PROCESS

INTRODUCTION

Ammonia is a chemically reactive gas that is very soluble in water and is much lighter than air (vapor density 0.59 of that of air). Cold vapor (e.g., from leaks) may however be denser than air. Although there have been incidents of exposure to harmful concentrations of ammonia in the world there have been few fatal accidents. Ammonia is characterized by a typical pungent odor and is detectable by most people at levels of about 5 ppm in the atmosphere. Although workers become tolerant to this effect and in the past have been able to work without distress at levels up to 70 ppm, currently the recommended exposure limit for ammonia is 25 ppm, 8 h timeweighted average (TWA) and the short-term exposure limit is 35 ppm, 10 min TWA. At 400 ppm, most people experience immediate nose and throat irritation, but suffer no permanent ill effects after 30–60 min exposure. A level of 700 ppm causes immediate irritation to the eyes, and a level of 1,700 ppm (0.17%) will give rise to repeated coughing and can be fatal after about 30 min exposure. Exposure to concentrations exceeding 5,000 ppm (0.5%) for quite short periods can result in death. Response to the effects of

Ó 2007 American Institute of Chemical Engineers

Ammonia is used as a refrigerant because of its particular thermodynamic properties, which enables it to move heat far more efficiently than other refrigerant gases such as halogenated hydrocarbons. It is particularly suited in the range of 0 to 2308C and hence is widely used for food preservation, the chilling of liquids, such as milk, beer and soft drinks, and in the chemical industry. New systems continue to be installed. A simple system theoretically needs four components (Figure 1) (1) evaporator, (2) compressor, (3) condenser, and (4) reducing valve. In practice other components such as an oil separator, intercooler, liquid receiver, surge drum, and liquid pumps
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Table 1. Acute toxicity: physiological response.

Response Immediate dangerous to life and health Minimal irritation Moderate irritation Definite irritation Cyclic hyperpnea/upper respiratory irritation, persistent Immediate irritation Dyspnea, convulsive coughing, chest pain, pulmonary edema may be fatal

Concentration (ppm) 500 5 9–50 125–137 500 (30 min) 700 1,500–10,000

Figure 2. Schematic representation of the refrigeration

system. A: ammonia storage tank, B: evaporator, C: compressor, D: oil separator, E: Condenser, F: Ammonia cylinder, P: pressure gauge, V1: ½ inch angle valve, V2: reducing valve, V3: ¼ inch globe valves, FW: flexible rubber hose.

INCIDENT 1

Figure 1. Simple flow diagram for ammonia refrigera-

tion system.

are often found. The useful refrigeration is produced at the evaporator. Liquid ammonia at low pressure, and hence low temperature, takes in heat by vaporizing. This vapor is removed by the compressor, which, in compressing it, raises the temperature from below to above ambient. The hot compressed gas gives up the heat by condensing to a liquid in the condenser. The high-pressure liquid then passes through the pressure-reducing valve to the evaporator. At the valve the liquid is cooled as some vapor flashes off. The remaining liquid is available for use in the evaporator. In a practical system it is likely there will be other items. An oil separator removes suspended oil carried over from the compressor and either returns it to the (pressurized) crankcase or holds it for draining in some way. There may be a multistage compressor with an intercooler. Bleeding high-pressure liquid into the low-pressure side cools this. Downstream of the condenser is generally a liquid receiver. Downstream of the reducing valve a surge drum is often found, which acts as a reservoir of cold liquid and evens out demand on the compressor and condenser. The liquid ammonia is drawn from the surge drum by a pump. Oil drains may be found on surge drums, liquid receivers, and elsewhere on large plants. There is also likely to be an automatic control system on all but the oldest and smallest plants.
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Rupture of Manifold During Transfer of Ammonia from Cylinder to Receiver Figure 2 shows the detail connection of the cylinder to the main line. From the ammonia cylinder (65 kg capacity) the ammonia is charged into the liquid line connected to the reducing valve, i.e., in the suction side of the ammonia compressor of an ice and cold storage plant. The aforementioned connection was made by a flexible rubber hose coupled by fixing nipples. The rubber hose burst and the ammonia leaked out. This operation was carried out on the night shift. The plant was located in a thickly populated area of Kolkata, West Bengal, India. Investigation of the incident found that the operator by mistake opened the valve (V1) attached to the ammonia receiver instead of opening the valve (V3) attached to the suction line of the ammonia compressor. The receiver pressure was about 15–18 kg/cm2, whereas the test pressure of the bursting manifold was 12 kg/cm2. So the manifold could not withstand the over pressure and bursted. As a safeguard for a possible release of ammonia in the compressor room, there was an exhaust fan arrangement in the compressor room for sucking ammonia out of the compressor room and discharged it to the bottom of the cooling tower. However, the outlet to the exhaust fan was, at the moment of the incident, dismantled for repair. Hence the ammonia at the outlet through the exhaust fan was not absorbed under water and this affected the inhabitants of the nearby houses. The connection between the ammonia cylinder to the system line was made by a flexible wire braided rubber hose coupled by fixing nipples. The charging line (leading to the said liquid line) was provided with a ¼ inch globe valve and a short piece of iron
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pipe to facilitate the charging operation. The ½ inch angle valve (V1) of the storage tank was open and the reducer valve (V2) was closed. As soon the worker opened the ¼ inch globe valve to ensure a vacuum in the rubber hose, it was observed that ammonia was coming out profusely from the junction point of the short iron pipe and the rubber hose where a crack of about 2 inch length was developed. The worker immediately fled away because of the vigorous leakage of ammonia and the leakage continued. It was also reported that immediately after the leakage started, the compressor was stopped. After a short while an operator approached the spot to close the globe valve connected to the said liquid line but failed as he was not provided with any suitable respiratory personnel protective equipment like self breathing apparatus. Immediately, two fire brigade engines arrived in the spot and the operator succeeded in closing the valves by using self-contained breathing apparatus from the fire brigade people. As ammonia is highly soluble in water, the fire brigade people sprayed large amounts of water to dissolve the ammonia. The effect of the leakage lasted for about 30 min. Nine female workers in an adjacent factory were affected and all of them were sent to a local hospital and were released after first aid treatment on the same day. Probable Causes of the Accident The probability of the dangerous occurrence of leakage is as follows: 1. During charging of ammonia from the ammonia cylinder to the liquid line, the bottom valve (½ inch angle type) of the ammonia receiver (3 ft O.D. and 12 ft long) remained open. The pressure inside the receiver was around 15–18 kg/cm2. As a result, liquid ammonia came out from the receiver to the liquid line because of backpressure, which escaped through the crack in the rubber hose. The rubber hose was designed to withstand up to 12 kg/cm2. 2. No self-containing breathing apparatus was provided and maintained in the factory to tackle the circumstances arising out of such accidental leakage of ammonia as a result of which the time span of leakage of ammonia lengthened. 3. There ware no water sprinklers in the compressor room to avoid any dispersion of ammonia gas from the compressor room to the outside. 4. The compressor room was not provided with any windows. Only three exhaust fans at a height of about 15 ft, located at the extreme west wall were provided and maintained which were not sufficient to ensure adequate ventilation in the room by circulation of fresh air.
INCIDENT 2

Figure 3. Schematic diagram of the oil separator

drum.

separator body (2 ft in diameter and 6 ft in height), probably because of a thread joint failure, resulting in a massive discharge of ammonia inside and outside the factory. Two workers with self-containing breathing apparatus entered the accident spot and isolated the oil tank. But the ammonia contained in the oil drum was completely drained. The entire plant was shut down for about 10 min after the start of the incident and a water sprinkler was also started. The situation was controlled partially with the help of the water sprinkler arrangement. Thirty workers were affected and all were transferred to a local hospital for treatment and release after first-aid. Probable Causes of the Accident 1. The incident occurred because of corrosion in the bottom line of the oil drum. 2. Corrosion was severe due to absence of preventive maintenance and due to presence of excessive moisture in the air, and also because of not carrying on periodic testing of those pipes, drains, and valves by any competent person. 3. All the pipelines and valves of the cold storage plant shall be periodically painted or made of stainless steel, to prevent corrosion effect.
HAZARD AWARENESS AND ITS REDUCTION

Oil Separator Drain Line Thread Failure—Massive Ammonia Leakage Through the Oil Separator in a Cold Storage Unit In the refrigeration unit, the drain line from the oil separator (Figure 3) suddenly detached from the oil
Process Safety Progress (Vol.27, No.1)

Ammonia is liquefied under pressure in refrigeration systems. Liquid ammonia released by accident may be in the form of an aerosol, i.e., small liquid droplets along with ammonia gas. It behaves as a dense gas even though it is normally lighter than air, i.e., and may travel along the ground instead of immediately rising into the air. This behavior may increase the potential risk for the exposure of workers and the public [3]. Ammonia vapors are not flammable at concentrations of less than 16%, but there may be fire and
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explosion hazard at concentrations between 16% and 25%. Mixtures involving ammonia contaminated with lubricating oil from the system, however, may have a much broader explosive range [3]. Fenton et al. [4] studied the influence of oil on the flammability limits of ammonia and they observed that oil reduced the lower flammability limit to as low as 8% depending on the type and concentration of oil. The following steps are recommended by the United States Environmental Protection Agency [3]: 1. Establish a training program for the workers to ensure that the ammonia refrigeration system is operated and maintained by knowledgeable personnel. 2. Consider using a spring-loaded ball valve (‘‘deadman’’ valve) in conjunction with the oil drain valve on all oil out pots (used to collect oil that leaks through seals) as an emergency stop valve. 3. Develop written safe operating procedures for removing oil from the oil out pots and also an in-house checklist procedure. 4. Remove refrigeration oil from the refrigeration system on a regular basis. 5. Provide barriers to protect refrigeration equipment, i.e., lines, valves, and refrigeration coils, from impact in areas where forklifts are used. 6. Develop and maintain a written preventive maintenance program and schedule based on the manufacturer’s recommendations for all of the refrigeration equipment. The preventive maintenance program should include : (i) compressors, (ii) pumps, (iii) evaporators, (iv) condensers, (v) control valves, (vi) all electrical safety(s) including—high pressure cutouts, high temperature cutouts, low pressure cutouts, low temperature cutouts, low oil pressure cutouts, (vii) ammonia detectors, (viii) emergency response equipment, including—air monitoring equipment, self-contained breathing apparatus, and air-purifying respirators. 7. Maintain a leak-free ammonia refrigeration system. Attention must be made to reports of an ammonia odor and all leaks repaired immediately. Leak test all piping, valves, seals, flanges, etc, should be carried out on regular basis (at least four to six times in a year). The methods for leak testing are sulfur sticks, litmus paper, or a portable monitor equipped with flexible probe is to be prepared for all times. 8. Consider installing ammonia detectors in areas where a substantial leak could occur. Ensure that the ammonia detectors are calibrated regularly against a known standard. Check the operation of ammonia sensors and alarms regularly. 9. Test the pressure relief valves on a periodic routine schedule. 10. Ensure that the ammonia refrigeration system is routinely monitored. 11. Keep an accurate record of the amount of ammonia that is purchased for the initial charge to the refrigeration system and the amount that is
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12. 13.

14.

15. 16. 17. 18.

replaced. Keep a record of the amount of lubricating oil added to the system and removed from the system. Ensure that refrigeration system lines and valves are adequately identified, e.g., by color coding or labeling by using an in-house system. Periodically inspect all ammonia refrigeration piping for failed insulation/vapor barrier, rust, and corrosion. Replace all deteriorated refrigeration piping as needed. Carry out regular inspections of emergency equipment and keep respirators, including airpurifying and self-contained breathing apparatus, and other equipment in good shape; ensure that personnel are trained in proper use of this equipment. Consider using the compressor room ammonia detector to control the ventilation fans. Prepare instructions for emergency shutdown procedure for the case of power failure. Establish written emergency procedures and instructions on what to do in the event of an ammonia release. Install remotely operated shut-off valves to stop the equipment or leaks from a distance.

PRECAUTIONS AGAINST TOXIC RISK

Respiratory Protective Equipment 1. Any person entering an area in which ammonia vapor is likely to be present at a significant level (e.g., for rescue or fault-finding purposes) must wear a self-contained or airline breathing apparatus. 2. Suitable full mask respiratory and eye protective equipment must be worn by every person carrying out engineering maintenance work on any system where there is a risk of release of ammonia. 3. Everyone who is likely to need to use respiratory protective equipment must be properly trained in its use and must be fully aware of its limitations. The equipment must be maintained, kept clean and examined at least once or twice a month. Appropriate records should be kept.

Evacuation and Emergency Procedures An emergency procedure is prepared which details the precise duties of all staff and the arrangements for evacuation, rescue, first aid, plant isolation, etc. Evacuation procedures are to be clearly set out and regularly practiced. A common method is to use the fire alarm provided that actuating points are immediately available at working areas. Personnel should be warned not to approach any vapor clouds. Adequate exits should be maintained from plant rooms at, all times. Personnel seriously affected by an ammonia escape suffer streaming eyes and violent coughing and rapidly become disorientated. They therefore require clear and prior knowledge of the safe exit route.
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Ventilation Compressor houses should be provided with adequate and suitable ventilation to meet the following requirements:  Normal ventilation should be provided to prevent build up of toxic concentrations of ammonia from leakage, i.e., from seals, glands, etc.  Emergency ventilation provisions should be made for sufficient mechanical ventilation to prevent flammable ammonia/air mixtures accumulating in the event of reasonably foreseeable plant or operational failure (e.g., valve failure). In such circumstances, the aim should be to keep concentrations below 25% of the lower explosive limit, i.e., 4% ammonia. Training in Plant Operation and Maintenance All personnel involved in the operation and maintenance of the plant must be adequately trained. The training should cover not only general principles of refrigeration but also specific points related to the particular plant. This applies as much to maintenance contractors as to an employer’s own staff.
ORGANIZATION FOR MEETING UP AN EMERGENCY

access both to the affected site and the outside road system so that the controllers could be reaching without any difficulty. The ECC should contain
• sufficient chairs, tables, and stationeries, • several telephones for internal and external

communication,
• the Material Safety Data Sheets of all chemicals

used on site,
• a computer with its all accessories with internet

facility for communication and data entry purposes, • radio contact with all sections of the plant, • log book, • important telephone numbers on the display board, • data pertaining to the decision making, • emergency lights, • canned food materials and beverages, • charts for communication network inside the plant and outside localities, • charts for dispersion distances, • diagram to assess weather category, and • layout map for escape routes, assembly points, location for personnel protective equipment, site entrance and road systems, medical centre location, location of fire extinguishers/materials etc.
Education and Training All personnel involved in the emergency response process must be trained to ensure a state of readiness for various situations. Training of all key personnel should be carried out regularly and also assess them regularly. Specific training programs are required to suit the requirement of the specialized personnel as, (a) fire, safety, and environmental personnel; (b) personnel department; (c) medical personnel; and (d) security personnel [6]. Testing of the Plan by Rehearsing Emergency plan procedures are to be developed and distributed to WMC, WIC, fire, safety and environmental, security, medical and personnel departments, and on-site emergency control room. The plan must be tested using models and necessary modifications incorporated. An actual mock drill should follow this exercise. The shortcomings and inadequacies in the plan must be identified and rectified accordingly. The mock drill should adequately address the on-site emergency plan, communication network and procedures, and coordination between various departments and their roles. On the basis of the mock drills, all suggestions from the various departments/observers/government agencies should be incorporated to prepare an updated version of the on-site emergency plan for both on-site and off-site.
CONCLUSION

In house planning, proper education for the local authority and communication with the surrounding neighbors is a must for the successfully handling of a plant emergency situation. It is not possible that only a group of personnel exclusively tackle the emergency situation. As such, the emergency team will be drawn from the following departments:
• maintenance, • fire, safety and environment, • personnel, • security, and • medical.

Communication The terminal manager or manager of the plant will act as the on-site works main controller (WMC). The shift manager/engineer in charge of the plant will act as the on-site work incident controller (WIC). The WIC should be very thoroughly familiar with the plant and be readily recognizable at the scene of the incident. On being alerted by the WIC, WMC takes charge of the situation, opening an emergency control room and operating there from. The WMC should be familiar with the plant and should have the necessary authority to make decisions regarding the affecting part the plant and the neighborhood. After the incidence, the incident identifier who first activated the emergency alarm shall report to the WIC on the location of the incident, probable quantity of chemical involved, probable extend of damage, wind direction and the actions taken at the site, if any. A communication network for the proposed [5] on-site emergency plan is given in Figure 4. Emergency Control Center [5] The emergency control center (ECC) should be located in a position of minimum risk and with good
Process Safety Progress (Vol.27, No.1)

This article deals with two accidents that occurred in a cold storage and ice-manufacturing factory due to failure of a hosepipe and a valve, causing leakage of ammonia gas from the plant. These accidents have
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Figure 4. Communication network of the proposed on-site emergency plan.

affected the work and outside environment and caused health injuries to the adjacent people. The causes of the accidents, the remedial measures, and the how to tackle the emergency situation have been discussed.

LITERATURE CITED

1. Y. Henderson and H.W. Haggard, Noxious Gases, Reinhold, New York (1943). 2. National Institute for Occupational Safety and Health, NIOSH Recommended Standard for Occupational Exposure to Ammonia., US Department of Health, Education, and Welfare, Rockville, MD, 1974.

3. United States Environmental Protection Agency, Report No. EPA 550-F-01-009 August 2001 [http:// yosemite.epa.gov/oswer/CeppoWeb.nsf/vwResources ByFilename/ammonia.pdf/$File/ammonia.pdf] 4. D. L. Fenton, K. S. Chapman, R. D. Kelley and A. S. Khan, Operating characteristics of a flare/oxidizer for the disposal of ammonia from and industrial refrigeration facility, ASHRAET Trans., 101 463–475 (1995). 5. B. V. Ramabrahman, B. Sreenivasulu and M. M. Mallikarjunan, Model on-site emergency plan. Case study: toxic gas release from an ammonia storage terminal, J. Loss Prev. Preven. Ind., 9(4) 259–265 (1996). 6. Web site: http://www.osha.gov/SLTC/ammoniare frigeration/evaluation.html

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